Protective agents against light rays

ABSTRACT

NEW 2- PHENYL- 4- (2&#39;&#39;,4&#39;&#39;- DIHYDROXYBENZOYL)-VTRIAZOLES AND ETHERS AND ESTERS OF THE 4&#39;&#39;-HYDROXY GROUP THEREOF ARE USED AS PROTECTIVE AGENTS AGAINST LIGHT RAYS FOR LIGHT-SENSITIVE ORGANIC MATERIALS. THEY ARE PREPARED BY DEALKYLATING THE CORRESPONDING 2-PHENYL-(2&#39;&#39;,4&#39;&#39;-LOWERALKOXYBENZOYL)-V-TRIAZOLES AND REACTING THE COMPOUNDS OBTAINED WITH ALKYLATING AGENTS OR ACYLATING AGENTS.

3,825,752 Patented July 30, 1974 int. Cl. F21v 9/06; G02b 5/20, 7/10 US.Cl. 252-300 10 Claims ABSTRACT OF THE DISCLOSURE New 2 phenyl 4 (2',4dihydroxybenzoyl)-vtriazoles and ethers and esters of the 4'-hydroxygroup thereof are used as protective agents against light rays forlight-sensitive organic materials. They are prepared by dealkylating thecorresponding 2-phenyl-(2,4-loweralkoxybenzoyl)-v-triazoles and reactingthe compounds obtained with alkylating agents or acylating agents.

This is a division of application Ser. No. 122,132, filed on Mar. 8,1971, now US. Pat. 3,749,732.

DETAILED DESCRIPTION The present invention relates to new2-phenyl-4-(2'-hydroxybenzoyl)-v-triazoles (1,2,3-triazoles), toprocesses for their production, and to their use as protective agentsagainst light rays for light-sensitive organic materials, the

protective agents protecting these materials against the harmful effectof the UV-rays of light, e.g. where the protective agents form aconstituent of protective filters against light rays, in that protectionis provided by the material to be protected being covered by film-likestructures or by protective layers which contain these triazolecompounds; or to the use of the compounds for the stabilising oflight-sensitive organic material, the v-triazole compounds beingincorporated into this material either homogeneously or on the surface.

Annularly-linked v-triazoles, especially benzotriazoles, have alreadyfrequently been suggested as protective agents against light rays, and,in some cases, have also been put on the market. Compared to this classof substances, the compounds according to the invention have, asprotective agents against light rays, a better fastness to light and, insome fields of application, a better com patibility with the substrateand better fastness to sublimation.

Of the compounds having an isolated triazole ring, 1,2,4-triazoles havealready been suggested as protective agents against light rays. Byvirtue of the inadequate fastness to light of these compounds of thisclass of substances, they are, however, not suitable as stabilisers. Onaccount of their often pronounced acceleration effect on thelight-produced yellowing of the substrates, they have hitherto acquiredno industrial importance.

Furthermore, also vi-triazoles with an isolated triazole ring are knownas protective agents against light rays. Surprisingly, it has now beenfound that 2-phenyl-4-(2'- hydroxybenzoyl)-v-triazoles of the followingformula I have a better protective action, particularly in the longwaveUV-range, a lower volatility, and a better compatibility with thesubstrates than these hitherto known v-triazoles.

The v-triazoles according to the invention correspond to the generalformula I:

In this formula:

R represents hydrogen, alkyl having 1 to 21 carbon atoms, cycloalkylhaving 5 to 10 carbon atoms, alkenyl having 3 to 18 carbon atoms,benzyl, alkylbenzyl having 8 to 11 carbon atoms, phenyl or alkylphenylhaving 7 to 10 carbon atoms,

R represents hydrogen, alkyl having 1 to 22 carbon atoms, A -alkenylhaving 3 to 18 carbon atoms, benzyl, alkylbenzyl having 8 to 11 carbonatoms or alkylcarbonyl having 2 to 18 carbon atoms, and

R" represents alkyl having 1 to 22 carbon atoms, or

chlorine, and

R represents alkyl having 1 to 22 carbon atoms, chlorine, hydroxyl oralkoxy having 1 to 22 carbon atoms,

n represents 0 to 3,

m represents 0 or 1, whereby n+m shall be 0 to 3.

Alkyl groups designated by R in formula I are, e.g.: methyl, ethyl,butyl, heptyl, undecyl, pentadecyl or heptadecyl. As the cycloalkylgroup, R represents, e.g. cyclohexyl, cyclopentyl or perhydronaphthyl.As the alkenyl group, R represents, e.g. A or A propenyl or A-hexadecenyl. If a benzyl group R is substituted by alkyl, this can bemethyl, ethyl, propyl, butal or ten.- butal. If R denotes alkylpheny],it can be, e.g. 4-methylphenyl, ethylphenyl or 4-tert.-butalphenyl.

Alkyl groups denoted by R in formula I can be, e.g.: methyl, ethyl,propyl, i-propyl, butyl, amyl, hexyl, octyl, decyl, dodecyl, tetradecyl,hexadecyl, oetadecyl or docosyl, whereby these alkyl groups can bebranched or unbranched.

A -alkenyl groups denoted by R are, e.g. A -propenyl,Z-methyl-[M-propenyl] or A -heptadecenyl. If a benzyl group R issubstituted by alkyl, it can be: methyl, ethyl, propyl, butyl orten-butyl. The alkylcarbonyl group can be, e.g.: acetyl, propionyl,2-ethylhexanoyl, caprylol, lauroyl, palmitoyl or stearoyl.

'In formula I, R" and R can denote identical or different alkyl groupssuch as, e.g. methyl, ethyl, i-propyl, n-butyl, tert.-butyl, n-octyl,1,1,3,3'tetramethylbutyl, dodecyl or oetadecyl, and R'" can be alkoxysuch as, e.g. methoxy, ethoxy, butoxy, octoxy, dodecyloxy, oroctadecyloxy.

In compounds of the general formula I which are particularly suitable asprotective agents against light rays:

R represents hydrogen, alkyl having 1 to 17 carbon atoms, phenyl oralkyl phenyl having 7 to 10 carbon atoms,

R' represents hydrogen, alkyl having 1 to 18 carbon atoms,

A -al kenyl having 3 to 4 carbon atoms, benzyl, alkylbenzyl having 8 to11 carbon atoms or alkylcarbonyl having 2 to 18 carbon atoms, and

R." represents alkyl having 1 to 8 carbon atoms or chlorine, and

R' represents alkyl having 1 to 8 carbon atoms, chlorine,

hydroxyl or alkoxy having 1-8 carbon atoms,

n represents 0 to 3,

m represents 0 or 1, whereby n+m shall be 0 to 3.

The new compounds of formula I wherein R represents hydrogen can beobtained by deal'kylation of compounds of the general formula II whereinR represents alkyl having -1 to 4 carbon atoms, and the remainingsymbols have the same meanings as those given under formula I;

and the new compounds of formula I wherein R represents alkyl having 1to 22 carbon atoms, A -alkenyl having 3 to 18 carbon atoms, benzyl,alkylbenzyl having 8 to 11 carbon atoms, or alkylcarbonyl having 2 to 18carbon atoms can be obtained by reaction of the compound obtained bydealkylation, the compound corresponding to the formula:

OH H I R C l i \N/ CH (RI/)n (Rlll)m with 1 equivalent of an alkylatingagent or acylating agent.

Mentioned as alkylating agents are: dialkylsulphates such as, e.g.dimethylsulphate or diethylsulphate, 1- bromo-, l-chloro'alkanes,2-bromoor 2-chloroalkanes such as, e.g. l-bromoethane, l-chloropropane,2-bromopropane, l-bromobutane, 1-bromo-3,3-dimethylpropane,1-chloro-3,B-dimethylbutane, l-bromohexane, 1-bromooctane,.l-bromodecane, l-bromododecane, l-bromotetradecane, l-bromohexadecaneor l-bromooctadeoane, benzyl chloride, 4-tert.butylbenzyl chloride,alkenylbromides or -chlorides such as, e.g. allyl chloride, allylbromide, methallyl chloride or methallyl bromide.

Mentioned as acylating agents are: acetic anhydride, aliphaticearboxylic acid chlorides such as, e.g. propionic acid chloride, valericacid chloride, Z-ethylcaproic acid chloride, caprylic acid chloride,laur-ic acid chloride, palmitic acid chloride or stearic acid chloride.

The alkylat-ion operations are performed in solvents, such as, e.g.alcohols, ketones or dimetbylacetamide, in the presence of acidacceptors such as, a.g. potassium carbonate, potassium hydroxide, orsodium methylate.

The acylation operations are performed under the conditions of theSchotten-Baumann-reaction. Compounds of formula II can be produced byconverting a compound of formula III:

(III) with, e.g. thionyl chloride into the corresponding carboxylic acidchloride, and reacting this, by means of a Friedel-Crafts reaction, witha compound of formula IV:

Used as compounds of formula are, e.g. resorcinolmonomethyl ether,resorcinol-dimethyl ether, resorcinoldiethyl ether, resorcinoldibutylether, resorcinol-dihexyl ether, resorcinol-d'ioctyl ether,resorcinol-didodecyl ether. The compounds of formula III can be obtainedby the following reactions:

1(a) The compounds of formula I'I'Ia:

all-1:0

(I{II) A (RI/I) (Illa) wherein 'R represents hydrogen, or

(b) The compounds of formula IIIb i R E-NH2 (Rll)n (Ix!!!)lzl (IIIb)wherein R represents alkyl C -C or phenyl, are subjected to acid oralkaline saponification, depending on the nature of the substituents R"and R', whereby, under correspondingly suitable reaction conditions,O-alkyl groups in the o-position are simultaneously dealkylated in the2-phenyl radical.

The compounds of formula IIIa are produced, e.g. by reaction of2-arylazornalonaldehydeoximes with agents splitting 01f water,preferably acetic anhydride under the Perkin reaction conditions.

The compounds of formula IIIb are produced, e.g. by the simultaneousreaction of 2-arylazoacylacetic esters with ammonia andcopper-(II)-salts, such as, e.g. copper- (II)-chloride-monohydrate, inalcohol at temperatures of around C. under pressure.

The compounds of the general formula I wherein R represents hydrogen,alkyl having 1 to 22 carbon atoms, benzyl, alkylbenzyl having 8 to 11carbon atoms, or alkylcarbonyl having 2 to 18 carbon atoms can also beproduced by a Fries rearrangement of a compound of the general formulacarrier substances, and are incorporated into the substrates or into thelight-filter base materials in amounts of 0.001 to 30 percent by weight,preferably 0.01 to percent by weight, relative to the carrier, wherebythis process can produce either purely physical mixtures or, where areaction occurs with the carrier, chemically modified protective agentsagainst light rays.

Naturally,,the v-triazoles according to the invention to be preferred aslight-filters are the ones producing the maximum light absorption.

The main carriers for the compounds of formula I according to theinvention are organic synthetic materials, i.e. polymeric organiccompounds, that is, thermoplastic and also thermosetting polymers.Thereby suitable are both fully synthetic polymers and natural polymers,as well as polymer-homologous chemical modification products thereof. Ofthe fully synthetic polymers, pure addition polymers and purecondensation polymers are particularly suitable, but also condensationpolymers crosslinked by addition polymerisation.

The addition polymers suitable as carrier materials for the newprotective agents against light rays can be put into the following maintypes:

(1) Homopolymers and copolymers of vinyl and vinylidene monomers whichhave been converted by radical, ionic, or metalorganic polymerisationinitiators into the corresponding polymers. Examples of such monomers,the polymerisates of which are suitable as carrier ma terials, are:

Polymerisable ethylenic unsaturated halogenated hydrocarbon compounds,especially vinyl chloride, vinyl fluoride and vinylidene chloride.

Polymerisable hydrocarbons with double-bond capable of addition,especially styrene, isobutylene, ethylene and propylene, whereby boththe atactic and the isotactic polymerisation forms are suitable.

m,fi-Unsaturated polymerisable carboxylic acids and functionalderivatives thereof, such as acrylic acid, methacrylic acid,acrylonitrile, alkyl esters, particularly lower alkyl esters, and amidesof acrylic and methacrylic acid, e.g. the methyl, ethyl, and butylesters of methacrylic acid and acrylic acid.

Polymerisable acyl derivatives of ethylenic unsaturated alcohols andamines, especially those of organic carboxylic acids, whereby aresuitable acyl radicals of alkanoic and alkenoic carboxylic acids havingup to 18 carbon atoms, and of aromatic monocyclic carboxylic acids suchas benzoic acids and phthalic acids, as well as acyl radicals of cycliccarbonic acid imides, such as, e.g. those of cyanuric acid. Examplesare: allyl phthalate, polyallyl melamines, vinyl acetate, vinylstearate, vinyl benzoate and vinyl maleate.

Polymerisable hydrocarbons with conjugated double bonds, such asbutadiene, isoprene, chloroprene.

(2) Homo and copolymers of epoxides, especially of bisepoxides, whichare formed by acidor base-catalytic hardening. Suitable in this class,for example, are polymerisates of bisglycidyl ethers of geminalbis-(p-hydroxyphenyl)-alkanes and -cycloalkanes.

(3) Homoand copolymers of lactams and lactones, particularly thepolymerisates of e-caprolactam.

(4) Homoand copolymers of aldehydes, especially of formaldehyde andacetaldehyde, such as polyoxymethylene and polyoxyethylene.

(5) Addition products of isocyanates with hydroxyl and/or aminocompounds, particularly such ones of dior polyisocyanates with biorpolyvalent hydroxyl or amino compounds. This class embraces thepolyurethanes and polyureas which are formed by reaction ofdissocyanates with polyesters and/or polyethers containing hydroxylgroups.

The condensation polymers suitable as carrier materials for thev-triazoles according to the invention are, among others, especiallypolyesters and polyamides. To be mentioned thereby are, in particular,linear thermoplastic polycondensates which, on the one hand, are derivedfrom dicarboxylic acids and organic dihydroxy derivatives or organicdiamines, and, on the other hand, from hydroxyor aminocarboxylic acids.Preferred linear polycondensates are the fibre-forming polymers ofw,w'-dicarboxylic acids and w,w'-dihydroxy compounds, or w,w'-diamines,as well as those of w-hydroxycarboxylic acids or of w-aminocarboxylicacids, particularly such polymers derived from saturated aliphatic,cycloaliphatic and carbocyclic nonannularly-linked aromatic carboxylicacids.

Especially suitable are the linear condensation products of thefollowing components: adipic acid hexamethylenediamine, sebacic acidhexamethylenediamine, terephthalic acid ethylene glycol, terephalicacid-1,4-dimethylolcyclohexane, IO-aminodecanecarboxylic acid,(ll-aminoundecylic acid).

Cross-linked polycondensates as carrier materials are thermosetting andare formed, in particular, by condensation of aldehydes with polyvalentcompounds capable of condensation. Mention is made of formaldehydecondensates with phenols, ureas and melamines.

Of the condensation polymers cross-linked by subsequent additionpolymerisation, those to be mentioned, in particular, are the polyesterresin, i.e. copolymerisates of polyesters of unsaturated organiccarboxylic acids, which contain double bonds capable of addition, withpolyvalent, especially bivalent alcohols, whereby, optionally, thesepolyesters are modified, on the one hand, with dicarboxylic acids notcapable of addition, and, on the other hand, with vinyl orvinylidenemonomers. Suitable monomers are preferably polymerisablemixtures of condensates of maleic acid, itaconic acid, citraconic acidwith bivalent alcohols, preferably the water-addition-products ofethyleneand propylene oxide, such as ethylene glycol, propylene glycoland diethylene glycol and, optionally, further dicarboxylic acids of thealiphatic-alicyclic and monocyclic-aromatic series, or their anhydridessuch as succinic acid anhydride, phthalic acid anhydride, and/or adipicacid, and of styrene and/or methyl methacrylate. This monomer mixture ofthe unsaturated polyesters and vinyland/or vinylidene-monomers (oftencalled liquid polyester resin) is preferably cross-linked by radicalpolymerisation initiators.

The natural polymers which are suitable as carrier materials for the2-phenyl 4 (2'-hydroxybenzoyl)-v-triazoles according to the inventionare, in particular, polysaccharides such as cellulose, or also rubberand proteins.

Of the polymerhomologously chemically modified synthetic polymers,mention is made, in particular, of the reaction products of polyvinylalcohols with aldehydes such as polyvinylbutyral, and of thesaponification products of polyvinyl esters. Polymerhomologouslychemically modified natural polymers as carrier materials for the newprotective agents against light rays are, in particular, celluloseesters and cellulose ethers, such as cellulose esters of acetic acid,propionic acid, benzoic acid, having, on average, 1 to 3 acyl groups perglucose unit.

The polymers listed in the foregoing constitute in the compositionsaccording to the invention, the polymers being either on their own or inadmixtures, the carriers of the new protective agents against lightrays. Particularly valuable compositions according to the inventioncontain, as carriers of the new protective agents against light rays,cellulose esters, polyester resins, polymethacrylic acid esters,polyvinyl chloride, polyethylene and polypropylene.

Also suitable as carrier materials for the new protective agents againstlight rays are, in addition to the above mentioned polymeric carriers,natural as well as synthetic light-sensitive waxes, fats and oils, andalso complex systems such as photographic material, emulsions containinglight-sensitive fatty substances, emulsions or dispersions of theaforementioned polymers.

The molecular weight of the aforestated polymers is of secondaryimportance, as long as it within the limits necessary for thecharacteristic mechanical properties of the respective polymers.Depending on the polymers, it can be 1,000 to several millions.Incorporation of 2- phenyl 4 (2' hydroxybenzoyl)-v-triazoles into thesepolymers is efiected, for example, depending on the nature of thepolymers, by at least one of these compounds and, optionally, furtheradditives such as, e.g. softeners, antioxidants, other protective agentsagainst light rays, heatstabilisers, and pigments, being worked into themelt by methods usual in engineering, either before or after beforepolymerisation, or by dissolving of the polymer moulding, or bydissolving in the corresponding monomer and additives in solvents whichare subsequently evaporated off.

The new protective agents against light rays may also be applied frombaths, e.g. from aqueous dispersions, or from solution in organicsolvents, to polymer granulate and to thinner carrier structures, suchas to films or threads.

Further additives are, e.g. antioxidants such as phenol compounds, forexample:

2,2'-thiobis- (4-methyl-6-tert.butylphenol);

4,4'-thiobis 3-methyl-6-tert.butylphenol)2,2-methylene-bis-(4-methyl-6-tert.butylphenol) 2,2-methylene-bis-4-ethyl-6-tert.butylphenol 4,4-methylene-bis-2-methyl-6-tert.buty1phenol) 4,4-butylidene-bis-3-methyl-6-tert.butylphenol) 2,2-methylene-bis- [4-methyl-6-('a-methylcyclohexyl phenol];

2,6-di-(2-hydroxy-3-tert.butyl-S-methylbenzyl)- 4-methyl-phenol;

1,1,3-tris-(4-hydroxy-2-methyl-5-tert.butylphenyl) butane;

1,3,5-trimethyl-2,4,6-tri-(3,S-di-tert.butyl-4-hydroxybenzyl -benzene;

esters of fl-4-hydroxy-3,S-di-tert.butylphenylpropionic acid with monoorpolyvalent alcohols such as methanol, octadecanol, hexanediol,trimethylolethane or pentaerythrite;

2,4-bis-octylmercapto-6-(4-hydroxy-3,5-di

tert.butylanilino)-s-triazine;

2,4-bis- (4-hydroxy-3,5-ditert.butylphenoxy)-6-0ctylrnercapto-s-triazine;

1, l-bis- (4-hydroxy-2-methyl-5-tert.butylphenyl)3-dodecylmercaptobutane;

4 hydroxy 3,S-di-tert.butylbenzylphosphonic acid ester,

such as diethyl or dioctadecyl ester;

(3-methyl-4-hydroxy 5 tert.butylbenzyl) malonic acid dioctadecyl ester;

s-(3,5-dirnethyl-4-hydroxybenzyl)-thioglycolic acid octadecyl ester;

amine derivatives, for example: phenyl-l-naphthylamine;

phenyl-2-naphthylamine; N,N'-diphenyl p phenylenediamine;N,N'-di-2-naphthyl-p-phenylenediamine; N,N'- di sec.butyl pphenylenediamine; 6-ethoxy-2,2,4'trimethyl-1,2-dihydroquinoline;6-dodecyl-2,2,4-trimethyl- 1,2-dihydroquinoline; monoanddioctyliminodibenzyl; polymerised 2,2,4-trimethyl-1,2-dihydroquinoline;

UV-absorbers and protective agents against light rays, such as (a)2-(2'-hydroxyphenyl)-benzotriazoles, e.g. the 5'- methyl-,3,S'-ditert.butyl-, 5-tert.butyl-, 5-chloro-3-, 5-ditert.butyl,5-chloro-3-tert.butyl-5'-methyl-, 3',5'- ditert.amyl-, 3'-methyl 5' Bcarbomethoxyethyl-, 5- chloro-3',5'-ditert.amyl-derivative;

(b) 2,4-bis(2-hydroxyphenyl)-6-alkyl-s-triazines, for example, the6-ethylor 6-undecyl-derivative;

(c) 2-hydroxybenzophenones, for example, the 4-hydroxy-, 4-methoxy-,4-octoxy-, 4-decyloxy-, 4-dodecyloxy-, 4,2, 4'-tri-hydroxyor2-hydroxy-4,4'-dimethoxyderivative;

(d) aryl esters of optionally substituted benzoic acids such as, forexample, phenylsalicylate; octylphenylsalicylate;

benzoylresorcinol; 3,5 di tert.butyl-4-hydroxybenzoicacid-2,4-di-tert.-butyl-phenyl ester; dibenzoylresorcinol;

(e) acrylates, for example, a-cyano-B,/3,diphenylacrylic acid ethylorisooctyl-ester; a-carbomethoxycinnamic acid methyl ester;a-cyano-fi-methyl-p-methoxycinnamic acid methylor butyl-ester; N-(fi-carbomethoxy-vinyD- Z-methylindoline;

(f) nickel compounds, for example: nickel complexes of2,2'-thiobis-(4-di-tert.octylphenol), such as the 1:1 and 2:1 complex,optionally with other ligands such as nbutylamine;nickeldibutyldithiocarbamate; nickel salts of 4 hydroxy 3,5di-tert.butylbenzylphosphonic acid monoalkyl esters such as methyl-,ethylor butyl-ester, the nickel complex ofZ-hydroxy-4-methylacet0phenoneoxime;

(g) oxalic acid diamides, e.g. 4,4'-di-octyloxyanilide; 2,2- dioctyloxy-5,5-di-tert.butyloxanilide;2,2'-di-dodecyloxy-S,5'-di-tert.butyloxanilide; metal-deactivators suchas monoand dihydrazides of monoand polybasic acids such as oxalic,adipic, salicylic, terephthalic or isophthalic acid; substitutedoxamides and oxanilides; N-salicyloyl-salicylaldehyde-hydrazone; nbutylbenZotriazole; tetrahydrobenzotriazole; Z-guanidinobenzimidazole;nucleation agents such as 4-tert.butylbenzoic acid, adipic acid,diphenylacetic acid; peroxide-decomposing compounds such as esters of,B-thiodipropionic acid, e.g. the lauryl, stearyl, myrystyl or tridecylester; salts of Z-mercaptobenzimidazoles, e.g. zinc salt;diphenylthiourea; phosphites such as triphenylphosphite;diphenylalkylphosphites; phenyldialkylphosphites;trinonylphenylphosphite; trilaurylphosphite; trioctadecylphosphite; 3,9diisodecyloxy 2,4,8,10-tetraoxa-3,9-diphosphaspiro- (5,5) -undecane;tri- (4-hydroxy-3,5-ditert. butylphenyl)-phosphite.

Other stabilisers such as potassium, barium, cadmium, magnesium, calciumor zinc salts of organic acids, e.g. stearates or laurates; basic orneutral lead salts of organic or inorganic acids; tin-containingstabilisers such as dibutyl tin laurates, -maleates or -mercaptides;hexamethylphosphoric acid triamide; copper salts such as copper acetatesor copper-I- or copper-II-halides, optionally in combination with alkalihalides, -hypophosphites, -phosphites and -phosphates or freephosphorous acids or phosphoric acid; manganese-II-salts, such as thechloride, hypophosphite or phosphate, optionally in combination withother hydrophosphites, phosphites and phosphates; dicyandiamide;diphenylurea.

Other additions such as softeners, antistatics, flameproofing agents,pigments, soot.

Inorganic fillers, e.g. asbestos, glass fibres, kaolin, talcum.

The light-sensitive materials can be protected from the harmful actionof light also by them being coated with a protective layer, e.g. with alacquer, containing at least one2-phenyl-4-(2'-hydroxybenzoyl)-v-triazole according to the invention; orby them being covered with structures containing such protective agentsagainst light rays, e.g. structures such as films, discs or plates. Inthese two cases, the amount of added protective agent against light raysis advantageously 10-30% (relative to the protective layer material) forprotective layers of less than 0.01 mm. thickness and 110% forprotective layers of 0.01- 0.1 mm. thickness.

In the case of certain modes of application, especially where hot chipsof polymer substances are being powdered with protective substances,products are particu larly valuable which melt above the softeningtemperature of the polymers concerned and which, nevertheless, aresufficiently soluble in the molten polymer.

The following examples illustrate the invention; the temperatures in theexamples are given in degrees Centigrade.

1 1 EXAMPLE 1 Production of2-phenyl-4-(2-hydroxy-4-methoxybenzoyl)-1,2,3-(2H)-triazole An amount of106 g. of 2-phenylazomalonaldehydeoxime, produced according to DRP947468 (1956), is added in portions, over a period of 30 minutes, to 400ml. of acetic anhydride heated to 60, whereby the temperature of thereaction mixture gradually rises to 70, the resulting exothermicreaction being completed after 1 hour. The mixture is then fully reactedover a period of 6 hours at the reflux temperature. After removal byevaporation in vacuo of excess acetic anhydride and formed acetic acid,the brown-coloured residue is recrystallised, with the aid of activecharcoal, from alcohol/ water. In this manner is'obtained2-phenyl-4-cyano-l,2,3-

(2H)-triazole in the form of colourless crystals, M.P. 94-95.

An amount of 85 g. of 2-phenyl-4-cyano-1,2,3-(2H)- triazole is refluxedin a mixture of 300 ml. of glacial acetic acid and 400 ml. ofhydrobromic acid (48%) for 12 hours, and the crystallisate, obtainedafter cooling to room temperature, washed with water and dried.Recrystallisation from chlorobenzene, with the use of bleaching earth,yields 2-phenyl-4-carboxy-l,2,3-(2I-I)-triazolein the form of colourlesscrystals, M.P. 187-189".

An amount of 94.5 g. of 2-phenyl-4-carboxy-1,2,3- (2H)-triazole issuspended in 200 ml. of chlorobenzene; to the suspension are added 200ml. of thionyl chloride, and the whole is heated to 80 until theevolution of gas has ceased. After cooling to room temperature,concentration by evaporation to dryness is carried out, and thecrystalline residue recrystallised from ligroin. By this means isobtained 2-phenyl-4-chlorocarbonyl-1,2,3- (2H)-triazole, M.P. 112, inthe form of colourless crystals.

An amount of 107 g. of 2-phenyl-4-chlorocarbonyl-1,2, 3-(2H)-triazoleisdissolved in 1,000 ml. of 1,1,2,2tetrachloroethane; to this solutionare then added in portions at temperatures of below 10, whilst stirringis proceeding, 138.2 g. of powdered aluminium chloride. To this reactionsolution are then added dropwise at 5-10", within 30 minutes, 69 g. ofrecorcin-dimethyl ether, and the internal temperature is subsequentlyslowly raised to 55, whereby the cleavage of hydrochloric acidcommences. The reaction is completed at about 60. The colour of thereaction solution hereby gradually changes to reddishyellow. Aftercooling to room temperature, the reaction solution is hydrolysed withice/hydrochloric acid, and the solvent removed by steam distillation.After washing with water and drying of the crude product,recrystallisation from glacial acetic acid is carried out and2-phenyl-4-(2- hydroxy 4 methoxybenzoyl)-l,2,3-(2H)-triazole, 173-175,obtained as yellowish crystals; A 343 mu, 6 13800.

If, instead of Z-phenylazomalonaldehydeoxime, equimolar amounts of2-(4-n-butylphenyl)-azomalonaldehydeoxime,2-(Z-methoxyphenyl)-azomalonaldehydeoxime, or2-(2,5-dichlorophenyl)-azomalonaldehydeoxime are used, the procedurebeing otherwise as described above, then by way of the following4-carboxytriazoles 1.1-1.3 are obtained, as intermediate products, theprotective agents against light rays 1.4-1.6.

1.1-2-(4-n-butylphenyl)-4-carboxy-1,2,3-(2H)-triazole,

1.22-(2-hydroxyphenyl) -4-carboxy-1,2,3- (2H) -triazole,

1.3-2-(2,5-dichlorophenyl) -4-carboxy-1,2,3- (2H) -triazole, M.P.190-192",

1.4--2- (4-n-butylphenyl -4-2-hydroxy-4-methoxybenzoyl)-1,2,3-(2H)-triazole, M.P. 94-95 Amax, 342 lmolar 16000,

1.52- (Z-hydroxyphenyl) -4-2-hydroxy-4-methoxybenzoyl)-1,2,3-(2H)-triazole, M.P. 146-147, k 346 l,molar 17000,

121.62-(2,5-dichloropheny1)-4-(2-hydroxy-4-methoxybenzoyl)-1,2,3-(2H)-triazole,M.P. 173-174, A 343 m,u emolar 11500.

EXAMPLE 2 Production of 2-phenyl-4-(2,4-dihydroxybenzoyl)-1,2,3- (2H)-triazole An amount of 28.1 g. of2-phenyl-4-(2-hydroxy-4-methoxybenzoyl)-1,2,3-(2H)-triazole (Example 1)is suspended in 300 ml. of benzene; to the suspension are added, wtihstirring, 40 g. of powdered aluminium chloride, the whole is heated toreflux temperature, and this temperature maintained for 2 hours. Aftercooling to room temperature, hydrolysis is performed withice/hydrochloric acid, the solvent removed by steam distillation, thefinegrained yellow reaction product washed with water, dried, andrecrystallised from chlorobenzene. In this manner is obtained 2 phenyl 4(2,4 dihydroxybenzoyl)-1,2,3- (2H)-triazole, M.P. 154-155 in the form ofyellow crystals, A 338 mu, amour 14900.

If, instead of 2-phenyl-4-(2-hydroxy 4methoxybenzoyl)-1,2,3(2H)-triazole, equimolar amounts of the compoundsstated in Example 1 under 1.4-1.6 are used, with the procedure otherwiseas described above, then the protective agents against light rays2.1-2.3 are obtained.

2.1-2-(4-n-butylphenyl)-4-(2,4-dihydroxybenzoyl)-1,2,3

iii-{)Ktrrazole, M.P. 118-119", Amax, 333 mp, 6

2.2-2-(2-hydroxyphenyl)-4-(2,4-dihydroxybenzoyl)- 1,2,3-(2H)-triazole,M.P. 187-188, X 333 mu, molar 2.32- 2,5 -dichlorophenyl) -4-(2,4-dihydroxybenzoyl) 1,2,3-(2H)-triazole, M.P. 200-201, A 333 m 1, E12200.

EXAMPLE 3 Production of 2-phenyl-4-(2-hydroxy-4-n-octyloxybenzoyl)-1,2,3-(2H)-triazole An amount of 25.6 g.of 2-phenyl-4-(2,4-dihydroxybenzoyl)-1,2,3-(2H)-triazole is dissolved in200 ml. of methanol; to this solution are then added 5 g. of sodiummethylate, the solution is concentrated by evaporation, and the residuedissolved in 300 ml. of dimethylacetamide. Whilst stirring ismaintained, 18.4 g. of l-bromooctane are then added dropwise at 20-40and, after the addition is completed, the reaction mixture is held for 4hours at After cooling to room temperature, the reaction product isprecipitated by the careful addition of dilute acetic acid. Afterwashing with water, and recrystallisation from acetonitrile is obtained2-phenyl-4-(2-hydroxy- 4-n-octoxybenzoyl)-1,2,3-(2H)-triazole in theform of slightly yellowish-coloured crystals, M.P. 82-83, k 343 m 614600.

If, instead of l-bromooctane, equivalent amounts of the below statedhalogen compounds are used, then the protective agents against lightrays given under 3.1-3.7 are obtained. For 3.1, 3.2 and 3.5 is used2-(4-n-butylphenyl)- 4 (2,4 dihydroxybenzoyl) 1,2,3 (2H) triazole(Example 2.1), for 3.4 is used 2-(2-hydroxyphenyl)-4-(2,4-dihydroxybenzoyl) 1,2,3 (2H)-triazole (Example 2.2), and for 3.7 is used2-(2,5-dichlorophenyl)-4-(2,4-dihydroxybenzoyl)-1,2,3-(2H)-triazole, theprocedure being in each case as described above.

3. 1-2- 4-n-butylphenyl -4-{2-hydroxy-4- [Z-methylpropenyl-(Z)]-oxybenzoyl}-1,2,3-(2H)-triazole; M.P. 107-108", X 342 mu, emolar16400,

3 .22- (4-n-butylphenyl) -4-[ 2-hydroxy-4-3-methylbutyl)-oxybenzoyl]-1,2,3-(2H)-triazole, M.P. 93- max. 342 l:molar 16700,

3.32phenyl-4-(2-hydroxy-4-decyloxybenzoyl)-1,2,3-

(2H)-triazolc, M.P. 83-84", k 343 mu, E 14500,

3 .4-2- Z-hydroxyphenyl -4-(2-hydroxy-4-tetradecyloxybenzoyl)-l,2,3-(2H)-triazole, M.P. 98-100",Amax, 347 m emolar 17800,

3.52-(4nbutylphenyl)-4-(2-hydroxy-4-octadecyloxybenzoyl)-1,2,3-(2H)-triazole,M.P. 74-75 A 340 mg, 6 16400,

3.62-phenyl-4- [2-hydroxy-4- (4-tert.butylbenzyl-oxybenzoyl]-1,2,3-(2H)-triazole, M.P. 8587, k

3 .7-2- (2,5-dichlorophenyl -4-2-hydroxy-4-octadecyloxybenzoyD-l,2,3-(2H)-triazole, M.P. 76-78", k 342D1,, emolar 12100.

EXAMPLE 4 Production of2-(4-n-butylphenyl)-4-(2-hydroxy-4-propionyloxybenzyl) -1,2,3-(2H)-triazole To a solution of 16.9 g. of 2-(4-n-butylphenyl)-4-(2,4-dihydroxybenzoyl)-1,2,3-(2H)-triazole (Example 2.1) and 3.96 g. ofpyridine in 75 ml. of dioxane are added dropwise within minutes, attemperatures below 4.63 g. of propionic acid chloride in 10 ml. ofdioxane. The reaction is completed in 2 hours at room temperature, andthe solution is subsequently heated for a further 10 minutes to 80. Itis then cooled to room temperature and the oil, precipitating as aresult of the addition of water, is taken up in methylene chloride; theorganic phase is washed successively with 2-n hydrochloric acid and withwater, dried over sodium sulphate, and the solvent evaporated off. Bycrystallisation of the residue from n-hexane is obtained 2(4-n-butylphenyl)-4-(2-hydroxy-4-propionyloxybenzoyl)-1,2,3-(2H)-triazoleas yellowish crystals, M.P. 128-129; A 342 mu, e 13900.

If, instead of 2(4-n-butylphenyl)-4-(2,4-dihydroxybenzoyl)-1,2,3-(2H)-triazole,equimolar amounts are used of2-(2-hydroxyphenyl)-4-(2,4-dihydroxybenzoyl)- 1,2,3-(2H) -triazole(Example 2.2), or2-phenyl-4-(2,4-dihydroxybenzoyl)-5-methyl-l,2,3-(2H)-triazole (Example6.7), and this reacted, according to the above directions, with stearicacid chloride or acetyl chloride, then the following protective agentsagainst light rays are obtained:

4.1-2-(2-hydroxyphenyl)-4-(2-hydroxy-4-stearoyloxybenzoyl)-1,2,3-(2H)-triazole,M.P. 95-96 343 m 6 13400,

4.22-phenyl-4- 2-hydroxy-4-acetoxybenzoyl -5-methyl-1,2,3-(2H)-triazole, M.P. 130-131 337 my, 6 11600.

EXAMPLE 5 Production of 2-(3-methoxyphenyl)-4-(2-hydroxy-4-dodecyloxybenzoyl)-1,2,3-(2H)-triazole An amount of 473 g. of 2 (3methoxyphenyl)-azomalonaldehydeoxime is reacted in 1,000 ml. of aceticacid anhydride, analogously to Example 1. After distillation in highvacuum is obtained, as yellowish oil solidifying in the receiver, 2(3-methoxyphenyl)-4-cyano-1,2,3-(2H)- triazole, B.P. 148-151 1.2 Torr.

An amount of 283 g. of 2-(3-methoxyphenyl)-4-cyano- 1,2,3-(2H)-triazoleis dissolved in 800 ml. of ethylene glycol monomethyl ether; to thissolution are added 430 g. of a 30% aqueous sodium hydroxide solution,and the whole is refluxed until the evolution of ammonia has ceased. Thereaction solution is then acidified, whilst being cooled with ice, with2-n hydrochloric acid, and the crude 2-( 3-methoxyphenyl -4-carboxy-1,2,3- 2H) -triazole dried after being washed with water.Recrystallisation from toluene yields colourless crystals, M.P. 149-151.

An amount of 265 g. of 2 (3-methoxyphenyl)-4-carboxy-1,2,3-(2H)-triazo1e is reacted with 250 m1. of thionyl 2 max.

chloride, analogously to Example 1, to give2-(3-methoxyphenyl)-4-chlorocarbonyl 1,2,3 (2H)-triazole.Recrystallisation from ligroin, with the aid of bleaching earth, yieldscolourless crystals, M.P. 75-76.

An amount of 23.8 g. of 2-(3-methoxyphenyl)-4-chlorocarbonyl-1,2,3-(2H)-triazole is disolved in 50 ml. of1,1,2,2-tetrachloroethane; to this solution are then added in portions,at temperatures below 10, 26.6. g. of powdered aluminium chloride. Tothe reaction mixture are subsequently added dropwise at 10, within 15minutes, 4 4.7 g. of resorcinoldidodecyl ether in 30 ml. of 1,l,2,2-tetrachloroethane, and the internal temperature is thereupongradually raised to 60, whereby the generation of hydrochloric acidoccurs. The reaction is completed at this temperature; as the reactionproceeds, the colour of the reaction solution changes to reddish-brown.After cooling to room temperature, hydrolysis with ice/hydrochloric acidis performed, and the solvent expelled by steam distillation. Afterwashing of the oily residue with water and crystallisation from acetone,crude 2-(3-methoxyphenyl) 4 (2 hydroxy 4 dodecyloxybenzoyl)- 1,2,3(2H)-triazole is obtained, which, after chromatography on silica gel[75-325 mesh, eluting agent benzene/hexane 1:9] is in the form ofslightly yellowish crystals melting at 79-80"; A 342 mu, 6 16140.

If, instead of resorcinoldidodecyl ether, equivalent amounts ofresorcinoldimethyl ether, resorcinoldipropyl ether and resorcinoldihexylether are used, then the protective agents against light rays 5.1-5.3are obtained. Instead of 2 (3 methoxyphenyl)-azomalonaldehydeoxime isreacted for 5.2: Z-phenylazomalonaldehydeoxime, and in the case of 5.3:2-(4-n-butylphenyl)-azomalonaldehydeoxime, the procedure in both casesbeing as described above.

5 .1-2- B-methoxyphenyl-4-:(2-hydroxy-4-rnethoxybenzoyl)-1,2,3-(2H)-triazole, M.P. 143-144, A340 molar 15000,

5.22-phenyl-'4 (2-hydroxy-4-n-propyloxybenzoyl 1,2,3-(2H)-triazole, M.P.121-122", x 342 mu, molar 141800,

5.3( 4-n-butylphenyl) -'4-(2-hydroxy-4-hexyloxybenzoyl)-l,2,3-(2H)-triazole, MJP. 91-92", Amax,342 Ill 1., emolar 16800.

EXAMPLE 6 Production of 2-phenyl-4 (2-hydroxy-4-methoxybenzoyl)-5-methyl-1,2,3-(2H)-triazole In a pressure vessel are heated, for I10hours at 150 g. of Z-phenylazoacetoacetic ester, g. of copper-('II)-acetate-monohydrate and 130 g. of ammonia gas in 2,000 ml. ofalcohol. After cooling of the reaction solution to room temperature,hydrogen sulphide gas is passed through the solution until the completeprecipitation of copper sulphide has occurred; the solution issubsequently treated with active charcoal in the boiling heat, andfiltered off. The solvent in the filtrate is evaporated off, and theresidue repeatedly recrystallised from alcohol. Thus obtained is2-phenyl-4-carbonamido-5-methyl 1,2,3- (2H)-triazole, M.P. 175-176", inthe form of colourless crystals.

An amount of 86 g. of 2-phenyl-4-carbonamido-5-rnethyl-"1,2,3-(2H)-triazole is refluxed in 400 ml. of a lzl-mixture ofglacial acetic acid and hydrobromic acid (48%) for 10 hours. Aftercooling to room temperature, the crude 2 phenyl4-carboxy-5-methyl-1,2,3-(2H)-triazole is precipitated by addition ofwater, and recrystallised from alcohol. Colourless crystals areobtained, M.P. 200-201.

-An amountof 65 g. of 2-phenyl-4-carboxy-5-methyl- 1,2,3-(2-H)-triazoleis suspended in ml. of toluene; to the suspension are added 200 g. ofthioyl chloride, and refluxing is performed until the generation of HClhas finished. After the reaction solution has been evaporated oif todryness, the residue is crystallised from ligroin,

15 whereby is obtained 2-phenyl-4-chlorocarbonyl-5-methyl1,2,3-(2H)-triazole, M.P. 110-111", in the form of colourless crystals.

58 g. of 2 phenyl 4-chlorocarbonyl-5-methy1-=l,2,3- (2H)-triazole, 70 g.of powdered aluminium chloride and 36.2 g. of resorcinoldimethyl etherare reacted in 400 ml. of 1,1,2,2-tetarchloroethane, as described inExample 1. After recrystallisation from toluene is obtained 2- phenyl 4(2 hydroxy 4 methoxybenzoyl)-5-methyl- 1,2,3-(2H)-triazole, M.P.l45-'146, in the form of slightly yellow coloured crystals, k 342 m 615260.

If, instead of 2-phenylazoacetoacetic ester, equimolar amounts of2-(2-methoxyphenyl)-azoacetoacetic ester, 2-(2-methoxyphenyl)-azostearoylacetic ester and 2-phenylazobenzoylaceticester are used, with the procedure other- Wise as described above, thenby way of the following 4- carboxytriazoles 6.1-6.3 are obtained, asintermediate products, the protective agents against light rays 6.4-6.6.

6. 12-(2-hydroxyphenyl) -4-carboxy-5-methyl-1,2,3-

(2H)-triazole, M.P. 214,

6.22- (2-hydroxyphenyl -4-carboxy-5-heptadecyl-1,2,3-

(2'H)-triazole, M.P. 115-116",

6.32-phenyl-4-carboxy-5-phenyl- 1,2,3- 2H) -triazole,

6.4-2-(2-hydroxyphenyl)-4-(2-hydroxy-4-methoxybenzoyl)-5-methyl-1,2,3-(2H)-triazole,M.P. 138-139", max. 348 l" molar 187501 6.5 2- (2-hydroxyphenyl -4-(2-hydroxy-4-methoxyb enzoyl)-5-heptadecyl-1,2,3-(2H)-triazole, M.P.93-94, max. 347 molar 18000,

6.62-phenyl-4-( Z-hydroxy-4-methoxybenzoyl)-5-pheny1-1,2,3-(2H)-triazole, M.P. 132-133 Amax, 337 m,u, e 14400.

The protective agents against light rays given under 6.7 to 6.9 wereobtained by demethylazation of the compounds of examples 6, 6.4 and 6.6respectfully, corresponding to the data in Example 2.

6.72-phenyl-4-(2,4-dihydroxybenzoyl)-5-methy1-1,2,3-

(2H)-triazole, M.P. 197-198, A 335 mu, amour 14200,

6. 82- (2-hydroxyphenyl) -4- (2,4-dihyroxybenzoyl) -5-methyl-1,2,3-(2H)-triazole, M.P. 180-181", A 338 mu, e 14700,

6.92-phenyl-4- (2,4-dihydroxybenzoyl)-5-phenyl-1,2,3-

(2H)-triazole, M.P. 205-206", Amax, 335 III/L, 5 16300.

EXAMPLE 7 Production of 2-pheny1-4-(2-hydroxy-4-dodecyloxybenzoyl)-5-methyl-1,2,3- (2H) -triazole 10 g. of2-phenyl-4-(2,4-dihydroxybenzoyl)5-methyl- 1,2,3-(2H)-triazole (Example6.7) are dissolved, together with 8.5 g. of l-bromododecane and 4.7 g.of potassium carbonate, in 150 ml. of dimethylacetamide, and thesolution is allowed to stand for 4 hours at 110. After cooling to roomtemperature, the reaction solution is acidified with dilute hydrochloricacid; the reaction product is then precipitated with water, washed, andrecrystallised from acetonitrile. In this manner is obtained2-phenyl-4-(2-hydroxy 4 dodecyloxybenzoyl)-5-methyl-l,2,3-(2H)-triazole,M.P. 108-109, as slightly yellow coloured crystals; A 342 mg, e 16280.

If, instead of l-bromododecane, the equivalent amount of the belowlisted alkyl bromides are used, then the protective agents against lightrays given under 7.1-7.5 are obtained. Instead of2-phenyl-4-(2,4-dihydroxybenzoyl) 5 methyl-1,2,3-(2H)triazole is reactedfor 7.2: (Example 6.8); for 7.4 and 7.5:2-phenyl-4-(2,4-dihydroxybenzoyl) -5-phenyl-1,2,3- (2H -triazole, thereaction being performed as specified.

l-bromoethane, l-bromooctane, l-bromohexadecane, l-bromooctadecane.

7. 12-phenyl-4- (2-hydroxy-4-octylbenzoyl) -5-methy1-1,2,3-(2H)-triazole, M.P. 94-95 A 342 m emomr 16100,

7 .22- (2-hydroxyphenyl) -4-(2-hydroxy-4-hexadecyloxybenzoyl)-5-methyl-1,2,3-(2H)-triazole, M.P.102-104", max. 348 l: molar 186007.3-2-phenyl-4-(2-hydroxy-4-octadecyloxybenzoyl)-5-methyl-l,2,3-(2H)-triazole, M.P. -97", A 340 l: molar 15450,

7.4-2-phenyl-4- (2-hydroxy-4-ethyloxybenzoyl) -5-phenyl-1,2,3-(2H)-triazole, M.P. 142-143", Amax, 337 my, molar 15100,

7.5-2-phenyl-4-(2-hydroxy-4-octadecyloxybenzoyl)-5-phenyl-1,2,3-(2H)-triazole, M.P. 91-92", k 334 III t, emolar 14900.

EXAMPLE 8 A solution of 15 g. of acetyl cellulose having on average 2.5acetoxy groups per glucose unit, and 0.075 g. of one of the UV-absorberslisted in the following table in 85 g. of acetone is spread out on aglass plate to form a film. The cellulose acetate films obtained afterevaporation of the acetone are dried firstly at room temperature, andthen in an oven at 60. Specimens of these 0.04 mm.- thick UV-filters areexposed, for measurement of the fastness to light of the UV-absorbers,for 500 hours in a Fade-O-Meter, and then examined with respect to theirresidual UV-absorption. The obtained results are given in the followingtable.

phenyl-1,2,3-(2H)-triazole:

EXAMPLE 9 Difficulty combustible liquid polyesterresin is polymerised,after the addition of 0.25% by weight of a UV-absorber from the tablebelow, with 1% by weight of benzoyl peroxide at a temperature of 80, toform 2.5 mm. thick sheets. The sheets are subsequently thermoset atSheets thus produced and then exposed exhibit appreciably less browningthan identically exposed sheets not containing the aforestatedUV-absorbers.

The applied polyester resin was produced as follows: To a mixture of g.of ethylene glycol and 292 g. of diethylene glycol is added in portions,at 80, a mixture of 343 g. of maleic acid anhydride and 428 g. oftetrachlorophthalic acid anhydride. After the air has been expelled inthe reaction vessel by nitrogen, the temperature is raised in the courseof 1 hour to 150", then in the course of 9 hours to 210, and thistemperature is maintained for a further hour. The mass is afterwardscooled to 180, vacuum is applied, and the pressure slowly reduced to 100Torr. These conditions are maintained until the acid number of thereaction mixture has sunk to below 50.

An amount of 100 g. of the thus obtained polyester is mixed with 50 g.of styrene, and the mixture is polymerised under the above describedconditions.

Similar results are obtained if, instead of tetrachlorophthalic acid,the equivalent amount of phthalic acid anhydride is used. In this case,however, the resulting polyester resin is not difiiculty combustible.

If, in the above process, the styrene is replaced by methylmethacrylate,then sheets are obtained which actually exhibit less inclination tobrown and which, moreover, are more easily stabilised.

Trans Percent mission transloss at mission 440 nm. at 440 after 1,000nm. hours of before Fade-O- expo- Meter Number UV-absorber sure exposureNone 89 25 2.2 2-(2-hydroxyphenyl)-4-(2,4-dihydroxy- 82.5

benzoyl)-l,2,3-(2H)-triaz0le. 6.7 2-phenyl4(2,4dihydroxybenzoyD-5- 84.0. 5

methyl-l,2,3-(2H)-triazole. 6.8 2-(2-hydroxyphenyl)r4-(2,4-dihydroxy-84. 5 0

benzoyl)-5-methyl-1,2,3-(2H)- triazole. 2.32-(2,5-diehlorphenyl)-4-(2,4-dihydroxy- 86 1. 5

benzoyl)-1,2,3-(2H)-triazole. 6 2-phenyl-4-(2-hydroxy-4-methoxy- 86 1. 5

benzoyl)-5-methyl-1,2,3-(2H)- triazole. 1.52-(2-hydroxyphenyl)-4-(2hydroxy-4- 84 1. 0

methoxybenzoyl)-1,2,3-(2H)- triazole. 1 2-phenyl-4-(2-hydrexy-t-methoxy-86. 5 2. 0

benzoyl) -1,2,3-(2H)-triazole. 2.1 2-(4-n-butylphenyl)-4-(2,4-dihydroxy-80 1. 5

benzoyl)-1,2,3-(2H)-triazole. 1.4 2-(4-n-butylphenyl)-4-(2-hydroxy-4- 862. 0

methoxybenzoyD-l,2,3-(2H)- triazole. 3.12-(4-n-buty1phenyl)-4-{2-hydroxy-4-[2- 84. 5 0. 5

methylpropenyl-(2)1-oxybenzoyl 1,2,3-(2H)-triazole. 3.2Z-(Qn-butylphenyl)-4-[2-hydroxy-4- 85.5 1.5

(Ii-methylbutyl)-oxybenzoyl]-l,2,3 (2H)-triazole.

Percent transmis sion of light of wave-length Number UV-absorber 340 nm.430 nm.

7.2 2-(2-hydroxypheny.)-4-(2-hydroxy-4- 2 92hexadecyloxybenzoyl)-5-metl1yl-1,2,3- (2H)-triazo1e. 3.72(2,5-dichlorophenyl) -4-(2-hydroxy-4- 2 92octadecyloxybenzoyl)-1,2,3-(2H)- triazole.

EXAMPLE 100 parts of methacrylic acid methyl ester, 0.5 parts of aUV-absorber from the following table, and 0.2 parts of lauroyl peroxideare mixed, and then polymerised at a temperature of 50-70 to form sheetsof 2 mm. thickness.

As can be seen from the following table, such sheets can be used asUV-filters.

18 EXAMPLE 11 Processed on a two-roller-mill in the usual manner intothe form of sheet is a mixture of:

parts of a suspension polyvinyl chloride (K-value 2.5 parts of a dialkyltin mercaptide stabiliser (Advastab) 17 M of the Deutschen AdvanceProduktion GmbH, Germany,

1.0 part of an epoxy stabiliser (Advablast 39 of the aforestated firm),

1.0 part of a wax used as lubricating and processing agent (Wax E of thefirm Farbwerke Hoechst, Germany), and

0.2 parts of a UV-absorber from the following table.

Specimens of these sheets are exposed for 2,000 hours in the XenotestExposure Apparatus, and then examined for discolouration. The resultsare given in the following table.

Appearance of the Number UV-Absorber exposed specimens None Dark-browndiscolouration of the whole specimen. 1.52-(2-hydroxyphenyl)-4-(2-hydroxy- Somewhat yellowish.

4-methoxybenzoyD-l,2,3 (2H)- triazole. 3.12-(4-n-butylphenyl)-4-{2-hydroxy- Isolated yellowish-2-phenyl-4-(2-hydroxy-4-dodecyloxybenzoyl)-5-methyl-1,2,3-(2H)-triazole.

6.5 2-(2-liydroxyphenyl)-4-(2-hydroxy- 4-methoxybenzoyl)-5-heptadecy11,2,3-(2H)-triazole.

brownish areas.

Yellowing commencing at isolated points.

7 Slightly yellowish.

Yellowish at isolated points.

If, instead of the aforementioned mixture, the following recipe is used:

100 parts of suspension polyvinyl chloride (K-value 62),

1.2 parts of a barium-cadmium-soap (Mark WS of S.A.

Argus Chemical N.V., Belgium),

0.5 parts of an organic phosphite (Mark C of the aforementioned firm),

1.0 part of a wax (Wax E of Farbwerke Hoechst, Germany) and 0.2 parts ofa UV-absorber from the following table,

the procedure being otherwise the same, then the results given in thistable are obtained.

100 parts of polyethylene having a density of 0.917 are homogeneouslymixed at in a Brabender-plastograph with 0.5 parts of a UV-absorber fromthe following table, and

0.5 parts of 3-(3',5'-di-t.butyl-4'-hydroxyphenyl)propionic acidoctadecyl ester.

19 The thus obtained mass is pressed in a platen press at 165 to form 1mm. thick sheets.

After weathering, these sheets exhibit, on being bent around 90,appreciably less tendency to be brittle than sheets without the additionof the additives in the table below.

benzoyl)-1,2,3-(2H)-triazole.

EXAMPLE 13 100 parts of polypropylene having a density of 0.90 arehomogeneously mixed at 220 in a Brabender-plastograph with 0.5 parts ofa UV-absorber from the following table,

0.2 parts of bis-(-t.butyl-4-hydroxy-2-methylphenyl)- sulphide,

0.2 parts of dilaurylthiodipropionate, and

0.2 parts of trioctadecylphosphite.

The thus obtained mass is pressed in a platen press at 180 to form 1 mm.thick sheets.

After weathering, these sheets exhibit, on being bent around 90",appreciably less tendency to be brittle than sheets produced otherwiseidentically, but without the addition of the protective agents againstlight rays contained in the following table.

Number UV-absorber 1.4 2(4-n-butylphenyl)4-(2-hydroxy-4-methoxybenzoyl)-1,2,3-(2H)-tn'azole 7.42-phenyl-4-(2-hydroxy4-ethoxybenzoyl)-5-phenyl-1,2,3-

(2H)-triazole 5.22-phen311-4-(2-hydroxy-i-n-propyloxybenzoyl)-1,2,3-(2H)- triazo e 42-(4-n-butylphenyl)-4-(Z-hydroxy--propionyloxybenzoyl)-1,2,3-(2H)-triazole 3.22-(4-n-butylphenyl)-4-[2-hydroxy-4-(3-methylbutyl)-oxybenzoyl]-1,2,3(2H) triazole 5.3 2-(4-butylphenyl)-4-(2-hydroxy-4-hexyloxyb enzoyl) 1,2,3-

(2H)-triazole 7.1 2-phenyl4-(Z-hydroxy-pctyloxybenzoyl)-5-methyl-1,2,3-

(2H)-trlazole 3.3 2-pgenyl-4-(2-hydroxy-4-deeyloxybenzoyl) -1,2,3-(2H)-5 2-(3-methoxyphenyl)4-(2-hydroxy-4-dodecylcxybenzoyl)- 1,2,3-(2H)triazole 3.4 2-(2-hydroxyphenyl)-4-(2-hydroxy-4-tetradecyloxybenzoyl)-1,2,3-(2H)-triazole 7.22-(2-hydroxyphenyl)-4-(2-hydroxy-4-hexadecyloxybenzoyl)-5-methyl-1,2,3-(2H)-triazole 3.7....2-(2,5-dichl0rphenyl)4-(2-hydroxyA-octadecyloxybenzoyD-1,2,3-(2H)-triazole EXAMPLE l4 Bleached maple-veneer is coated with awood-lacquer of the following composition:

15.0 parts by weight of cellulose acetate (of the firm Bayer inLeverkusen, Germany) having a ca. 56% acetic acid content,

10.0 parts by weight of dimethyl glycol phthalate,

1.0 part by weight of2-phenyl-4-(2-hydroxy-4-dodecyloxybenzoyl)-5-methyl 1,2,3 (2H)-triazole(Exam- P 5.0 parts by weight of methyl alcohol,

10.0 parts by weight of toluene, and 50.0 parts by weight of ethylacetate.

The natural yellowing of the wood is prevented by this lacquer.

EXAMPLE 15 A cosmetic preparation protecting against light rays isobtained as follows:

5 parts of white ceresin wax,

22 parts of white petrolatum,

19.5 parts of white mineral oil,

15 parts of lanolin, free from water,

2 parts of2-(4-n-butylphenyl)-4-(2-hydroxy-4-hexyloxybenzoyl)-1,2,3-(2H)-triazole(Example 5.3),

36 parts of Water,

0.5 parts of perfume.

The ceresin, petrolatum and lanolin are melted together and theprotective agent against light rays dissolved in the melt. The mineraloil is thereupon added at 70, and subsequently the water slowly workedin at the same temperature. Stirring is continued until the temperaturehas fallen to below 50, whereupon the perfume is added.

EXAMPLE 16 A sprayable cosmetic protective agent against light rays isobtained by dissolving in parts of ethanol,

10 parts of ricinic acid methyl ester,

10 parts of oleyl alcohol, and

1 part of2-(4-n-butylphenyl)-4-(2-hydroxy-4-hexyloxybenzoyl)-l,2,3-(2H)-triazole(Example 5.3).

(Rll)n (RH/)m wherein R is hydrogen, alkyl having 1 to 21 carbon atoms,cycloalkyl having 5 to 10 carbon atoms, al-kenyl having 3 to 18 carbonatoms, benzyl, alkylbenzyl having 8 to 11 carbon atoms, phenyl oralkylphenyl having 7 to 10 carbon atoms,

R is hydrogen, alkyl having 1 to 22 carbon atoms, A -al'kenyl having 3to 18 carbon atoms, benzyl, alkylbenzyl having 8 to 11 carbon atoms oralkylcarbonyl having 2 to 18 carbon atoms,

R" is alkyl having 1 to 22 carbon atoms or chlorine, and

R is the same as R", hydroxyl or alkoxy having 1 to 22 carbon atoms,

n is O to 3,

m is 0 or 1, and

n+m is 0 to 3.

2. A composition as claimed in claim 1 wherein the organic material ishornoand copolymerisates derived from styrene, vinyl chloride, vinylfluoride, acrylonitrile, olefins, acrylic acid esters and/or methacrylicacid esters, in polyesters, polyamides, polyester resins, polyacetals,polycarbamates, polyurethanes, cellulose ethers, or cellulose esters.

21 3. A composition as claimed in claim 1 wherein the organic materialare cellulose esters, polyester resins, polymethacrylic acid esters,polyvinyl chloride, polyethylene, polypropylene, or polystyrene.

4. A composition of claim 1 wherein in the stabilizer R is hydrogen,alkyl having 1 to 17 carbon atoms, phenyl or alkylphenyl having 7 to 19carbon atoms,

R is hydrogen, alkyl having 1 to 18 carbon atoms,

n -alkenyl having 3 or 4 carbon atoms, benzyl, alkylbenzyl having 8 to11 carbon atoms, or alkylcarbonyl having 2 to 18 carbon atoms,

R" is alkyl having 1 to 18 carbon atoms or chlorine,

and

R'" is the same as R", hydroxyl or alkoxy having 1 to 8 carbon atoms,and

n is to 3,

m is 0 or 1, and

n+m is 0 to 3.

5. A composition of claim 1 wherein in the stabilizer R is hydrogen,alkyl having 1 to 17 carbon atoms, or

phenyl,

R is hydrogen, alkyl having 1 to 18 carbon atoms,

A -alkenyl having 3 or 4 carbon atoms, benzyl, alkylbenzyl having 8 to11 carbon atoms, or alkylcarbonyl having 3 to 18 carbon atoms,

R" is butyl or chlorine, and

R' is the same as R", hydroxyl or alkoxy,

n is 0 to 2,

m is 0 or 1, and

n+m is 0 to 2.

References Cited UNITED STATES PATENTS 3,642,813 2/1972 Kirchmayer etal. 260-308 A 3,575,956 4/1971 Cronse 252-300 3,551,449 12/ 1970Szmuszkovic 252-300 RONALD H. SMITH, Primary Examiner J. P. BRAMMER,Assistant Examiner US. Cl. X.R. 260-308

